Organic sulphonated hydrogenated abietyl derivatives and method of producing



Patented Feb. 20, 1940 r 2,190,734

UN ITED STATES PATENT OFFECE- ORGANIC SULPHONATED HYDROGENATED ABIETYLDERIVATIVES 'AND'ME'EHOD OF PRODUCING Alfred L, Rummclsburg, Wilmington,Del., assignor to Hercules Powder Company, Wilmington, Del., acorporation of Delaware No Drawing. Application September 10, 1937,Serial No. 163,325

16 Claims. ((31. 260-98) This invention relates to organic salts ofhyhydropiinaryl alcohol and tetrahydropimaryl a1- drogenated Rosinylsulphonates and to methods cohol related to pimaric acid, or mixtures ofthese fortheir production. I alcohols; and the corresponding alcohols ormix- The method in accordance with this invention tures of alcoholssimilarly related to the various consists of sulphonating hydrogenatedRosinyl other rosin acids. '5 alcohol, or another hydrogenated Rosinylderiv- Dihydroand tetrahydroabietyl' alcohols may ative by treatmentwith a suitable sulphonatbe obtained, for example, by catalytichydrogenaing agent, and then reacting the hydrogenated tion of alkylabietates, or alkyl esters of wood Rosinyl sulphonate with an organicbase. Thus, rosin, crude or refined, or the corresponding hy- I maytreat a hydrogenated Rosinyl alcohol with drogenated esters, all as ismore fully disclosed a sulphonating agent, such as, for example, sulinthe application for United States patent, Serial phuric acid, sulphurtrioxide, chlorsulphonic acid, No. 604,859, filed April 12, 1932, byIrvin W.

acetyl sulphuric acid, etc., to produce hydrogen Humphrey, or by meansof the action of sodium ated Rosinyl sulphonate which is then reactedupon an alcohol solution of hydrogenated methyl with an organic base.Again, I may react a or ethyl abietate according to the methoddehydrogenated Rosinyl halide with a sulphite, such scribed by Ruzickaand Meyer, l-lelf, Chim. Acta as, for example, sodium sulphite, sodiumacid 5, 581-93 (1922) for the unhydrogenated abiesulphite, etc., andthen react the resulting prodtates. The corresponding halides, as, forexamuct with an organic'base. ple, dihydroabietyl chloride and bromide,tetra" The organic base which I utilize may be, for hydroabietylchloride and bromide, etc., may be 20 example, heterocyclic nitrogencompounds, as, produced by treating the alcohol with the desiredpyridine, quinoline, etc.; aliphatic amines, as, hydrogen halide, ashydrogen chloride, hydrogen methylamine, ethylamine, triethylamine;aliphatbromide, etc., or with phosphorous trior pentaic alkolamines, as,triethanolamine, etc,; arochloride, phosphorous tribromide, etc.

matic amines, as, aniline, naphthylamine, ethyl A method for thepreparation of a hydrogenat- 25' anil ne, e ced Rosinyl alcohol may beillustrated by the fol- The hydrogenated Rosinyl derivatives referredlowing procedure in which hydrogenated abietyl to herein and in theclaims as suitable for sulalcohol is prepared by the catalytic reductionof phonation may be represented as C19H31CH2X, hydrogenated methylabietate:

C19H33CI-I2X, or mixtures thereof, where X is One hundred twenty g.hydrogenated methyl 30 OH, Cl, Br, or other functional groupreplaceabietate are placed in a pressure bomb equipped able insulphonation by the sulphate or sulwith electric heating, hydrogeninlet, agitator, phonate group. It will be understood that where andpyrometric secondary devices, 4 g. copper- X is an OH group, thederivative is a hydrogenchromium oxide catalyst are added and H2 gasated Rosinyl vaJCOhOlallowed to enter and leave several times in order.35

y the term hydrogenated ROSiIIYI 81001101 s to flush out oxygen. Thebomb is then filled with mean? a primary alcohol Obtained by thehydrogen to a pressure of about 172Gb sq. in. boxylic reduction of ahydrogenated rOSin acld, Electric heating and agitation is started andsugh for example abletic acid sapimc acid about 3 hours is required forthe bomb to reach pimaric acid; a primary alcohol obtained by the itsmaximum temperature of AS follows 40 simultaneous carboxylio reductionand hydro- (typical run): genation of a rosin acid; or a primary'alcoholobtained by the carboxylic reduction of a rosin acid and thehydrogenation of the alcohol so Time 22 52 532 55 produced. The termhydrogenated Rosinyl al- 45 cohol, includes within its scope, forexample, a hydrogenated abietyl alcohol, which may be dihydroabietylalcohol (C19H31CH2OH) or 'tetra- 250 2920 hydroabietyl alcohol(CwHssCHzOI-I) related to 5o abietic acid (C19H29COOI-I). It alsoincludes 276 2300 within its scope the corresponding hydrogenatedsapinyl alcohol, which may be dihydrosapinyl al- 276 2210 cohol ortetrahydrosapinyl alcohol related to M 276 2240 sapinic acid, ormixtures of these alcohols; the hydrogenated pimaryl alcohol, which maybe 61- Agitation and heating is stopped and the sys- 55 tem allowed tocool to 25 C. The pressure is then #1000. The gas is bled off, and theproduct extracted with ether, filtered from catalyst, and the ether thenevaporated. The product contains 89% hydrogenated abietyl alcohol.

The copper-chromium oxide catalyst used in the above procedure isdesirably prepared according to the method described by Connor, Folkersand Adkins, J. A. C. S. vol. 54, pages 1139-40. The hydrogen pressureutilized may range from about 50 to 2000 atmospheres, and temperaturefrom about 175 to 350 C.

The raw material for conversion to hydrogenated abietyl alcohol may, inplace of hydrogenated methyl abietate, be wood rosin, esters of woodrosin, as methyl abietate, ethyl abietate,

. alcohol.

butyl abietate, propyl abietate, etc., abietic acid, abietic acid estersor other abietyl compounds containing a group reducible to the primaryalcohol group, CHZOH.

The various other hydrogenated Rosinyl alcohols may be prepared by theabove procedure by the substitution of other types of rosin for woodrosin or by the substitution of the alkyl esters of other rosin acidsfor the alkyl abietates used in the above procedure. Thus, hydrogenatedsapinyl alcohol may be prepared by substituting the 'alkyl sapinates,the alkyl esters ofv American gum rosin, for the alkyl abietates.Likewise, hydrogenated pimaryl alcohol may be prepared from the alkylesters of pimaric acid, the alkyl esters of French gum rosin.

Other resin acids of similar structure may be employed or their esters,to synthesize various resin alcohols. If desired, the rosin prior toconversion maybe partially distilled under reduced pressure separating acut of say 515% to increase the resin acid content of the residue whichaccordingly will yield a hydrogenated Rosinyl alcohol of higher puritythan the original rosin.

If desired wood rosin or one of the gum rosins may be refined prior toconversion, as by distillation under reduced pressure according to knownprocedures, and the distillate or one of its cuts used as the source ofhydrogenated Rosinyl The rosin may also be given a prior refining bycrystallization from a suitable solvent or by washing in solution, asgasoline, with a substantially immiscible selective color-body solvent,as, furfural, phenol, methyl thiocyanate or ethyl thiocyanate, for theremoval of color-bodies and other impurities.

The hydrogenated Rosinyl alcohol may be purifled, if desired, by meansof fractional distillation at reduced pressure, distilling 01f apreliminary cut of say 5l5% which may be low in hydrogenated abietylalcohol, depending upon the conditions of hydrogenation and source ofraw material.

The main portion of the hydrogenated Rosinyl alcohol may be distilledunder reduced pressure, if desired,'to improve its color and removetraces of catalyst, if such be present. During the distillation severalcuts of the distillate may be' made. The raw material may behydrogenated to its dihydroor tetrahydroabietyl compound, or a mixtureof the two, prior to reduction to hydrogenated abietyl alcohol. In theevent that the unsaturated bonds in the raw materials are not partiallyhydrogenated in a separate operation, prior to the reduction of thecarboxyl group to the alcohol group, the'latter procedure normallyresults in a partial saturation of the unsaturated bonds of the abietylcompound with hydrogen. Thus, methyl abietate will yield dihydroabietylalcohol.

It is also to be realized that the crude products of the abovereactions, comprising mixtures of the various hydrogenated Rosinylalcohols may be sulphonated in accordance with this invention withoutsubstantial purification. For example, a technical grade of hydrogenatedabietyl alcohol comprising alcohols of varying degrees of hydrogenationand obtained by hydrogenation as above described of alkyl abietates maybe treated in accordance with this invention without furtherpurification. Such technical grades may have a total hydrogenatedabietyl alcohol content of about 50%, but desirably for treatment inaccordance with this invention will contain from 80-95 hydrogenatedabietyl alcohols.

- The non-alcohol content is probably a C19 cyclic hydrocarbon.

The products in accordance with this invention will comprise, dependingupon the particular hydrogenated Rosinyl derivative and sulphonatingagent employed, various organic base salts of hydrogenated Rosinylsulphonate and/or sulphates or mixtures thereof. The distinction betweenthe sulphonates and the sulphates is purely technical:

In the sulphonates the linkage to carbon is directly through the sulphuratom. While in the sulphate the linkage is from carbon to oxygen. Theprocess in accordance with this invention, especially whereonlypartially saturated Rosinyl derivatives are employed, may produceorganic base salts of mixed sulphonates and sulphates, since there areseveral reactive positions in the Rosinyl'radical besides the positionoccupied by the functional group and, accordingly, several differentreactions with the sulphonating agent may take place. However, since allthese organic base salts of the sulphates, sulphonates and mixturesthereof are substantially equivalent in the various uses made of them,they will be referred to hereinafter and in the claims as organic basesalts of hydrogenated Rosinyl sulphonation products, which term is meantto include both the organic base salts of the hydrogenated Rosinylsulphonates, the sulphates and mixtures thereof.

The organic base salts of the sulphonated hydrogenated Rosinylderivatives produced in accordance with this invention are soluble inpetroleum and aromatic hydrocarbons. They are brownish colored solidscontaining from about 2% to about 16% sulphur and are highly useful asdispersive, emulsifying and wetting-out agents.

The method in accordance with this invention requires no special form ofapparatus and includes broadly the treatment in any suitable manner of ahydrogenated Rosinyl derivative with a sulphonating agent and thenneutralizing the sulphonation product so formed with an organic base.Thus, for example, the hydrogenated Rosinyl derivative, as an abietylalcohol, may be slowly added to the sulphonating agent, as for example,concentrated sulphuric acid, with vigorous agitation. The ratio ofalcohol to acid may. be widely varied, for example, from 1:02 to 1:50parts by weight, and the reaction temperature may be varied within Widelimits, for example, from about 20 C. to about 200 0., although atemperature of from about 10 C., to about 40 C. is preferred. Theagitation will be continued after the addition of all the alcohol untila test portion of the mixture is completely soluble when dropped intowaterabout 6 to 20 hours at room temperature. The mixture is thendiluted with water while cooled and agitated to give an acidconcentration of 30 to 70%.. The free sulphonation product will separateas the upper layer on standing and is purified by being dissolved inwater, neutralized with an organic base, salted out with, for example, asaturated solution of sodium chloride or sulphate, and dried.Alternately, the free sulphonation product may be washed with asaturated salt solution, such as an aqueous solution of an electrolytesalt, as, sodium chloride, sodium sulphate, etc., and then neutralizedwith an organic base.

The sulphonated, hydrogenated Rosinyl derivative will ordinarily beneutralized by the addition of an amount of the organic base slightly inexcess of the amount theoretically necessary for neutralization.However, when using an organic base to which indicators, such as litmusand the like, are sensitive, the end-point of the neutralizationreaction may be determined by the aid of a suitable indicator.

If desired the sulphonating agent, as, for example, fuming sulphuricacid, chlorsulphonic acid, etc. may be added to the hydrogenated Rosinylderivative, for example, a hydrogenated Rosinyl alcohol, dissolved in asuitable non-reactive solvent, such as ether, petroleum ether hexane,carbon tetrachloride, dichloro ethyl ethyl ether, etc., or in a solventsuch as acetic anhydride, glacial acetic acid, etc., which combines withthe sulphuric acid to form acetylsulphuric acid, a sulphonating agent.The acid will desirably be added in excess of the amount theoreticallynecessary and may be added in considerable excess. Where a waterimmiscible solvent such as carbon tetrachloride is used, and the amountof sulphonating agent employed is not greatly in excess of theoretical,the reaction mixture can be treated with the requisite organic base forneutralization. The solvent may then be removed by distillation atatmospheric or reduced pressure, holding the temperature below about 100C. to prevent decomposition of salt.

Where either no solvent is employed, or the solvent used is watersoluble, such as acetic acid, the reaction mixture can be treated withan excess of a saturated solution of a salt such as, NaCl, Na2SO4, etc.,for washing. The viscous sulphonated material may then be neutralizedwith the organic base.

Drying of the organic base salt will desirably proceed below atemperature of about 100 C. to prevent decomposition.

Where a non-alcohol, hydrogenated Rosinyl derivative, as for example, ahydrogenated Rosinyl halide, is employed, the sulphonating agent willdesirably be a sulphite or acid sulphite, as, for example, sodiumsulphite, sodium acid sulphite, etc. The hydrogenated Rosinyl halidedissolved in a suitable solvent, as, for example, benzene, xylene,petroleum hydrocarbons, ether, etc. will be treated directly with thesulphite at a suitable temperature, as, for example, from about 10 C. toabout 275 C. The use of a neutral sulphite will produce directly thecorresponding salt of the sulphonated hydrogenated Rosinyl derivative,while an acid sulphite will produce the usual acidic sulphonationproduct which will be neutralized with an organic base. If a hydrocarbonsolvent is employed, the sulphonation product will separate and can beeasily removed. If a solvent in which it is soluble, e. g. ether, C014,or the like, is used, the sulphonation product may be readily obtainedby evaporation 150 parts by weight of hydrogenated abietyl Z10 alcoholwere dissolved in 400 parts by weight of carbon tetrachloride and themixture cooled to about 0 C. The mixture was maintained at this lowtemperature and 66 parts by weight of chlor- '15 sulphonic acid addedslowly with rapid stirring over a period of thirty minutes. When thechlorsulphonic acid was added, the resulting reaction mixture wasdivided into three parts, and

neutralized, respectively, with three diiierent organic bases asfollows:

One-third of this reaction mixture was, neutralized with commercialtriethanolamine, which consists of about 75% triethanolamine, 20%

diethanolamine, about 5% monoethanolamine and a small amount of water.After neutralization the product was recovered by distilling off thecarbon tetrachloride on a steam bath. The small amount of water presentis removed along with the carbon tetrachloride. The resulting trioethanolamine salt of hydrogenated abietyl sulphonate was alight-colored, pasty mass which was hygroscopic in nature and difiicultto dry completely. It was soluble in water, pine oil and petroleumhydrocarbon solvents. It was soluble in pine oil to a somewhat greaterextent than the corresponding sodium salt. Solutions of this salt inpine oil gave a suds when shaken with water.

One-third of the sulphonation reaction mixture 0 was neutralized withpyridine. The carbon tetrachloride and water contained therein was thenremoved by distillation on a steam bath to yield a pasty, hygroscopicproduct which was soluble in water and petroleum hydrocarbons. Thisproduct was the pyridine salt of hydrogenated abietyl sulphonate. Thesolution of this salt in naphtha gave suds when shaken with water.

One-third of the sulphonation reaction mixture was neutralized withaniline. The carbon tetrachloride and water were removed by distillationon a steam bath to yield a pale-colored, pasty, hygroscopic productwhich was diflicult to dry. This product is the aniline salt ofhydrogenated abietyl sulphonate. It is practically insoluble in water,but is soluble in petroleum hydrocarbons. A petroleum hydrocarbonsolution gives no appreciable suds when shaken, but will emulsifyreadily in water.

Example II About 290 g. of hydrogenated abietyl alcohol are slowly addedto 500 g. of concentrated H2SO4 at 5-10 C. with vigorous agitation.After the alcohol is added, the mixture is agitated from A to 10 hoursat room temperature, until sub- 5 stantially complete solubility inwater results. The reaction mixture is slowly poured into a mixture ofice and water with agitation and cooling. sulphonated, hydrogenatedabietyl alcohol separates and is washed with several 1000 cc. portions70 of 12% NaCl solution, then dissolved in about 500 cc. of water andneutralized with about 142 g. of commercial triethanolamine. Thetriethanolamine salt of hydrogenated abietyl sulphonate is salted fromsolution by adding about 500-1000 cc.

of 12% NaCl solution, and dried by heating at a temperature below C.

Example III About 290 g. of hydrogenated abietyl alcohol are mixed withg. of acetic anhydride; to the mixture are slowly added 300 g. ofconcentrated H2804 with cooling and vigorous agitation. The temperatureis held at about 10 C. while introducing the acid. After the acid hasbeen introduced, the agitation is continued at room temperature from to10 hours until complete water solubility results. The reaction mixtureis then poured into a mixture of 500 g. of water and ice, with coolingand agitation. The sulphonated material separates and is washed withseveral 1000 cc. portions of 12% NaCl solution, then dissolved in about500 cc. of water and neutralized with about 84 g. of pyridine. Thepyridine salt of hydrogenated abietyl sulphonate is salted from solutionby adding 500-1000 cc. of 12% NaCl solution and. dried by heating at atemperature below 100 0.

Example IV About 290 g. of hydrogenated abietyl alcohol are dissolved in600 g. of petroleum ether, and 116 g. of chlorsulphonic acid are addedslowly with vigorous agitation while keeping the temperature at 5-10' C.After the acid is added, about 84 g. of pyridine is added with coolingand agitation, and the solvent removed by distillation on the steambath. The resulting pyridine salt of hydrogenated abietyl sulphonate isdried by heating at a temperature below 100 C.

This application is a continuation-in-part of my copending applicationSerial No. 215,941 filed March 16, 1934 (now United States Patent No.2,107,508)

What I claim and desire to protect by Letters Patent is:

1. A salt of an organic nitrogen-containing base and the sulphonationproduct of a hydrogenated Rosinyl alcohol.

2. A salt of an organic nitrogen-containing base and the sulphonationproduct of a hydrogenated abietyl alcohol.

3. An aliphatic alkalolamine salt of the sulphonation product of ahydrogenated Rosinyl alcohol.

4. An aliphatic alkalolamine salt of the sulphonation product of ahydrogenated abietyl alcohol.

5. An ethanolamine salt of the sulphonation product of hydrogenatedabietyl alcohol.

6. A triethanolamine salt of the sulphonation product of hydrogenatedabietyl alcohol.

'7. A salt of a heterocyclic nitrogen-containing product of ahydrogenated Rosinyl alcohol which includes reacting a Rosinyl alcoholwith a sulphonating agent and neutralizing the sulphonated product withan organic nitrogen-containing base.

14. The method of producing an organic nitrogen-containing base salt ofthe sulphonation product of a hydrogenated Rosinyl alcohol whichincludes reacting a suitable Rosinyl alcohol and a sulphonating agent inthe presence of a solvent for the hydrogenated Rosinyl alcohol, andneutralizing the sulphonated product with an organic nitrogen-containingbase.

15. The method of producing an organic nitrogen-containing base salt ofthe sulphonation product of a hydrogenated Rosinyl alcohol whichincludes reacting a suitable Rosinyl alcohol and a sulphonating agent inthe presence of an inert, water-immiscible solvent, neutralizing thesulphonation product with an organic nitrogen-containing base, andrecovering the organic nitrogencontaining base salt of the sulphonated,hydrogenated Rosinyl alcohol by evaporating the said solvent.

16. The method of producing an organic nitrogen-containing base salt ofthe sulphonation product of a hydrogenated Rosinyl alcohol, whichincludes reacting a suitable Rosinyl alcohol and a sulphonating agent inthe presence of a watermiscible solvent, separating the acidicsulphonation product from the reaction mixture by the addition of asolution of an electrolyte salt, and neutralizing the said acidicsulphonation product with an organic nitrogen-containing base.

ALFRED L. RUMMELSEURG.

